WO2001094433A1 - Water swellable compositions - Google Patents
Water swellable compositions Download PDFInfo
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- WO2001094433A1 WO2001094433A1 PCT/EP2001/005994 EP0105994W WO0194433A1 WO 2001094433 A1 WO2001094433 A1 WO 2001094433A1 EP 0105994 W EP0105994 W EP 0105994W WO 0194433 A1 WO0194433 A1 WO 0194433A1
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- acrylates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
Definitions
- This invention relates to pourable liquid compositions which are radiation curable comprising an ethylenically unsaturated polymer having radiation polymerisable functionality dissolved in a monomer, the compositions being water swellable upon radiation curing.
- Films or fibres may also be prepared in-situ via common coating or spinning techniques which usually involve polymerising hydrophilic monomers in solvents such as water. Similarly they can be applied as coatings to fabrics or other articles by many of the usual water or solvent based coating techniques.
- US-A-4, 167,464 and US-A-4,486,489 describe the use of photopolymerisation methods to prepare water absorbent films or fibres from aqueous formulations comprising pre-formed acrylic acid salts as the main component. Since large amounts of water are present in the formulations the speed of the acrylate polymerisation is reduced and this can leave films which are very soft and/or which have a high level of residual tack if the systems are under- cured or not dried by insufficient exposure to the radiation and/or post heating. Indeed there may be relatively higher residual unreacted monomers if not fully cured. In addition such films, after cure, contain relatively high residual water which can be regarded as undesirable per se eg in cables.
- the invention provides pourable liquid compositions which are radiation curable comprising an ethylenically unsaturated polymer having radiation polymerisable functionality dissolved in a monomer, the compositions being water swellable upon radiation curing.
- composition may be used within a wide range of relative proportions and comprise:
- composition may additionally comprise:
- composition may further comprise:
- additives include coupling agents, air release agents, inhibitors, wetting agents, lubricants or waxes, stabilisers, antioxidants and pigments.
- compositions of desirable formulations will depend on a number of factors including the required processing speed, coating thickness, water swelling or blocking response in terms of speed and extent, the nature of the surfaces to which the coating is to be applied, and the nature of solutions in which it is required to function (ie absorb).
- the radiation polymerisable polymer which may be referred to as a prepolymer, as in a polymer which contains ethylenic unsaturation such that it can be further polymerised, may be formed in two stages. Firstly, a monomer or monomers selected from groups below may be polymerised to form a polymer backbone, then secondly unsaturated functionalities are introduced into the polymer backbone. This unsaturated functionality provides the prepolymer with the radiation polymerisable functionality.
- the polymer backbone may be formed from monomer or monomers selected from groups consisting of:
- alkyl (meth) acrylates preferably C, to C 5 alkyl (meth) acrylates, eg methyl methacrylate;
- - (meth) acrylates having mono- or multi- carboxylic acid or sulphonic acid functionality eg acrylic acid or anhydride, ss-carboxy ethyl acrylate (ss-CEA), maleic acid, fumaric acid or itaconic acid (or anhydrides thereof);
- HAA hydroxy ethyl acrylate
- HEMA hydroxy ethyl (meth) acrylate
- HPA hydroxy propyl acrylate
- acrylated epoxides eg glycidyl (meth)acrylate, acrylated amino alcohols and alkoxylated amines such as those which may be prepared in-situ by simple mixing of, for example, acid functional acrylate and a hydroxyl functional primary amine
- - acrylamide and its derivatives eg N-hydroxymethylacrylamide, N-tris(hydroxymethyl)methyl acrylamide, other N-alkyl or N-alkoxy substituted acrylamides eg N,N-dimethyl acrylamide and acrylamide derivatives such as acrylamidosulphonic acid and its salts;
- polyether (meth) acrylates such as monoacrylates having alkoxylated chains eg ethoxy or poly ethylene oxide structure e.g. polyethylene glycol monoacrylates, preferably methoxy polyethyleneglycol 350 methacrylate, polypropylene glycol monoacrylates (egSR 607 from Sartomer Co), ethoxy ethoxyethyl acrylate (EOEOEA), ethyltriethylene glycol methacrylate, ethoxylated phenoxy ethyl acrylate, monomethoxy neopentyl glycol propoxylate monoacrylate (Photomer 8127 from Henkel);
- monoacrylates having alkoxylated chains eg ethoxy or poly ethylene oxide structure
- polyethylene glycol monoacrylates preferably methoxy polyethyleneglycol 350 methacrylate
- polypropylene glycol monoacrylates egSR 607 from Sartomer Co
- EEOEA ethoxy ethoxyethy
- - amino- (meth) acrylates or amine- (meth) acrylate salts eg N,N-dimethylaminoethyl acrylate (DMAEA), tertiary-butylaminoethyl methacrylate; hydrochloride or toluene sulphonate or other salt of DMAEA;
- Preferred polymer backbones i.e. the prepolymer as it exists before the introduction of unsaturated functionalities, are formed from monomers selected from groups consisting of:
- alkyl (meth) acrylates preferably C, to C 5 alkyl (meth) acrylates, eg methyl methacrylate;
- - (meth) acrylates having mono- or multi- carboxylic acid or sulphonic acid functionality eg acrylic acid or anhydride, ss-carboxy ethyl acrylate (ss-CEA), maleic acid, fumaric acid or itaconic acid (or anhydrides thereof); - (meth) acrylates having a hydroxy functional group eg.
- HAA hydroxy ethyl acrylate
- HEMA hydroxy ethyl (meth) acrylate
- HPA hydroxy propyl acrylate
- acrylated epoxides eg glycidyl (meth)acryiate
- acrylated amino alcohols and alkoxylated amines such as those which may be prepared in-situ by simple mixing of, for example, acid functional acrylate and a hydroxyl functional primary amine
- - acrylamide and its derivatives eg N-hydroxymethylacrylamide, N-tris(hydroxymethyl)methyl acrylamide, other N-alkyl or N-alkoxy substituted acrylamides eg N,N-dimethyi acrylamide and acrylamide derivatives such as acrylamidosulphonic acid and its salts;
- polyether (meth) acrylates such as monoacrylates having alkoxylated chains eg ethoxy or poly ethylene oxide structure e.g. polyethylene glycol monoacrylates, preferably methoxy polyethyleneglycol 350 methacrylate, polypropylene glycol monoacrylates (egSR 607 from Sartomer Co), ethoxy ethoxyethyl acrylate (EOEOEA), ethyltriethylene glycol methacrylate, ethoxylated phenoxy ethyl acrylate, monomethoxy neopentyl glycol propoxylate monoacrylate (Photomer 8127 from Henkel);
- monoacrylates having alkoxylated chains eg ethoxy or poly ethylene oxide structure
- polyethylene glycol monoacrylates preferably methoxy polyethyleneglycol 350 methacrylate
- polypropylene glycol monoacrylates egSR 607 from Sartomer Co
- EEOEA ethoxy ethoxyethy
- - amino- (meth) acrylates or amine- (meth) acrylate salts eg N,N-dimethylaminoethyl acrylate (DMAEA), tertiary-butylaminoethyl methacrylate; hydrochloride or toluene sulphonate or other salt of DMAEA;
- Polymer backbones of particular interest are copolymers comprising:
- methyl acrylate 0.01 to 5 mole % of methyl acrylate, ethyltriethylene glycol methacrylate or methoxy polyethyleneglycol 350 methacrylate.
- the most preferred polymer backbone comprises:
- the method of introduction of the unsaturated functionality's into the polymer backbone may include various known methods, which include:
- the unsaturated acid chloride is preferably (meth)acryloyl chloride.
- acryloyl chloride may react with an amine group of the polymer backbone, in order to introduce an unsaturated amide functionality into the polymer backbone.
- An alternative method involves the acid chloride monomer being copolymerised into the polymer backbone.
- the backbone is then reacted with an unsaturated monomer which contains a reactive hydrogen atom, such as those attached to oxygen, nitrogen or sulfur.
- the unsaturated monomer may be a (meth)acrylate having mono- or multi- hydroxy functional group(s), an amino- (meth) acrylate or an amine- (meth) acrylate salt.
- the unsaturated monomer is preferably selected from hydroxy ethyl methacrylate or tertiary- butylamino ethyl (meth)acryiate.
- acryloyl chloride may be a monomer on the polymer backbone, which is then reacted with a (meth) acrylate having mono- or multi- hydroxy functional group(s), such as 2-hydroxy ethyl methacrylate, in order to introduce an unsaturated ester functionality into the polymer backbone.
- a (meth) acrylate having mono- or multi- hydroxy functional group(s) such as 2-hydroxy ethyl methacrylate
- a preferred method of introducing the unsaturated functionality is to functionalise a polymer backbone which comprises a tertiary-butylaminoethyl methacrylate unit using acryloyl chloride.
- the monomeric anhydride may be an acrylic anhydride, preferably maleic anhydride or itaconic anhydride.
- maleic anhydride may react with a hydroxy group of the polymer backbone, in order to introduce an unsaturated ester functionality into the polymer backbone.
- An alternative method involves the monomeric anhydride monomer being copolymerised into the polymer backbone.
- the monomeric anhydride is preferably an acrylic anhydride.
- the backbone is then reacted with an unsaturated monomer which contains a reactive hydrogen atom, such as those attached to oxygen, nitrogen or sulfur.
- a preferred method of introducing the unsaturated functionality is to functionalise the polymer backbone which comprises a maleic anhydride monomer with 2-hydroxyethyl (meth)acrylate.
- the monomeric epoxide may be an acrylated epoxide, preferably glycidyl methacrylate.
- glycidyl methacrylate may react with an amine group of the polymer backbone, in order to introduce an unsaturated functionality into the polymer backbone.
- An alternative method involves the monomeric epoxide being copolymerised into the polymer backbone.
- the monomeric epoxide is preferably an acrylated epoxide.
- the backbone is then reacted with an unsaturated monomer which contains a reactive hydrogen atom, such as those attached to oxygen, nitrogen or sulfur.
- the unsaturated monomer may be may be a (meth)acrylate having mono- or multi- hydroxy functional group(s), an amino- (meth) acrylate or an amine- (meth) acrylate salt.
- the unsaturated monomer is preferably hydroxy ethyl methacrylate or tertiary-butylamino ethyl (meth)acrylate.
- glycidyl methacrylate may be a monomer on the polymer backbone, which is then reacted with 2-hydroxyethyl methacrylate in order to introduce an unsaturated functionality into the polymer backbone
- a preferred method of introducing the unsaturated functionality is to functionalise the polymer backbone which comprises a glycidyl methacrylate monomer with 2-hydroxyethyl (meth)acrylate.
- the polymer backbone may undergo an esterification or transesterification reaction. Hydroxy groups on the polymer backbone may be esterified with an unsaturated acid, preferably (meth)acrylic acid.
- Carboxylic acid groups on the polymer backbone may be esterified with an unsaturated hydroxyl containing monomer, preferably a (meth)acrylate having mono- or multi- hydroxy functional group(s), more preferably hydroxyethyl (meth)acrylate.
- An ester group contained within the polymer backbone may undergo a tranesterification reaction with an ester.
- a methyl acrylate monomer within the backbone may undergo reaction with a (meth)acrylate having mono- or multi- hydroxy functional group(s), preferably hydroxy ethyl acrylate.
- the polymer backbone may contain a tertiary amine group, which is quatemised with an unsaturated chloride.
- a preferred unsaturated chloride is allyl chloride.
- the preferred unsaturated functionality is a vinyl functionality.
- the prepolymer may comprise from 1 to 50 unsaturated bonds, preferably the prepolymer comprises 1 to 20. More preferably the prepolymer comprises 5 to 10 unsaturated bonds.
- the prepolymer may be charged, for example as a result of a quatemisation reaction to introduce an unsaturated functionality into the polymer backbone.
- Preferred prepolymers of the present invention are anionic or cationic, more preferred prepolymers possess a cationic charge.
- the scope of the invention is not limited to compositions comprising charged prepolymers, the prepolymer may be non-ionic. Any charge which does exist on the prepolymer may be neutralised by the inclusion of an organic acid in the composition.
- the organic acid may be any organic acid which is soluble in the monomer contained in the composition. Such acids include carboxylic acids and sulfonic acids. Preferred organic acids include citric acid, adipic acid and benzoic acid.
- the presence of organic acid will affect the final pH of the composition, which may be any value.
- Preferred pH values are in the range of pH 4 to pH 12. More preferably, the pH of the composition is not lower than pH 6.
- any water which comes into contact with the composition will result in swelling, but the organic acid will also be ionised, thus neutralising the charged prepolymer. Any water which comes into contact before the curing of the composition will also ionise the organic acid, resulting in the neutralisation of the charged prepolymer.
- the composition may comprise between 10 to 90 % of the prepolymer, based on the total weight of the composition, preferably between 30 to 70 % by weight and most preferably between 40 to 60 % by weight.
- the molecular weight of the prepolymer may range from 1000 to 500,000. Preferably the molecular weight is below 100, 000, and more preferably the molecular weight ranges from 5000 to 40,000.
- the monomer in which the polymer is dissolved is preferably liquid in the temperature range of 10 to 40 degrees C, most preferably liquid at room temperature.
- the monomer in which the polymer is dissolved may be selected from the following:
- - (meth) acrylates having mono- or multi- hydroxy functional group(s) eg. hydroxy ethyl acrylate (HEA), hydroxy ethyl (meth)acryiate (HEMA), hydroxy propyl acrylate (HPA), hydroxy propyl (meth)acrylate (HPMA) ; glycerol mono-acrylate; trimethylolpropane mono- acrylate, acrylated epoxides eg glycidyl methacrylate, acrylated amino alcohols and amino poiyols and alkoxylated amines for example, acid functional acrylate and a hydroxyl functional primary amine such as tris(hydoxymethyl)aminomethane; - acrylamide and its derivatives eg N-hydroxymethylacrylamide, N-tris(hydroxymethyl)methyl acrylamide, other N-alkyl or N-alkoxy substituted acrylamides eg N,N-dimethyl
- polyether (meth) acrylates such as monoacrylates having alkoxylated chains eg ethoxy or poly ethylene oxide structure e.g. polyethylene glycol monoacrylates, preferably methoxy polyethyleneglycol 350 methacrylate or methoxy polyethyleneglycol 550 methacrylate, polypropylene glycol monoacrylates, ethoxy ethoxyethyl acrylate (EOEOEA), ethyltriethylene glycol methacrylate, ethoxylated phenoxy ethyl acrylate, monomethoxy neopentyl glycol propoxylate monoacrylate (Photomer 8127 from Henkel);
- monoacrylates having alkoxylated chains eg ethoxy or poly ethylene oxide structure
- polyethylene glycol monoacrylates preferably methoxy polyethyleneglycol 350 methacrylate or methoxy polyethyleneglycol 550 methacrylate
- polypropylene glycol monoacrylates ethoxy ethoxye
- N- unsaturated N-substituted amides eg N-vinyl formamide, N-vinyl caprolactam, N-vinyl pyrolidone.
- Preferred monomers include N,N-dimethylacrylamide, N-vinyl formamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and ethyltriethylene glycol methacrylate.
- the most preferred monomer being N,N-dimethylacrylamide.
- a single monomer or a blend of monomers selected from those listed above, may be used in the composition.
- One or more photoinitiators may be selected from the groups below:
- photoinitiators are aryl diazonium salts or aryl sulphonium salt, and aryl metal complexes such as Ciba CG24-061 "RTM”.
- the composition may comprise between 0.01 and 20 % by weight of photoinitiator, based on the total weight of the composition, preferably between 2 and 12 % by weight.
- bases examples include hydroxides, alkoxides, carbonates, carbamates, and hydrogen carbonates, di- and tri- basic phosphates or citrates, - of ammonium and of Group I and II metals including sodium, potassium, magnesium, and calcium.
- Organic bases such as amines eg triethanolamine or triethylamine (TEA) or morpholines (eg Nmethylmorpholine, MeM) or piperidines or tris(dimethylaminomethyl)phenol can also be used.
- TAA triethanolamine or triethylamine
- morpholines eg Nmethylmorpholine, MeM
- piperidines tris(dimethylaminomethyl)phenol
- Bases are usually added to compositions containing acid functional acrylates.
- added salts examples include halides, acetates, sulphates, carboxylated and phosphates of metals and ammonium or other amine/substituted ammonium counter- ions.
- solvents which may be added include alcohols, glycols polyols, ethers and alkoxylated solvents.
- examples include ethanol, methanol, isopropanol, ethylene glycol, propylene glycol, polyalkylene oxides, glycerol, trimethylolpropane, alkoxylated derivatives and ethers of the above (e.g. Photonols from Henkel).
- Levels of added solvents, if used, are preferably lower than 25% by weight of the total composition.
- the present compsositions preferably contain no solvent. Water may also be used as a solvent. However, the present compsositions preferably contain no water.
- Example surfactants which can be used with or without water can be non-ionic, eg alkoxylated amines, alcohols, esters, oils, fatty acids, nonylphenol and ethanolamides and sorbitan esters, alkyl aryl polyether alcohols eg Triton X100 "RTM" (from Rohm & Haas), or anionic or cationic, or amphoteric.
- Surfactants can help to stabilise same systems with dispersed salt or base or other undissolved solid.
- blowing agent which can generate gas when contacted with water or on heating (eg during exposure to U V lamp and/or other application source of heat) can increase the swell response in some cases.
- a blowing agent which can generate gas when contacted with water or on heating (eg during exposure to U V lamp and/or other application source of heat) can increase the swell response in some cases.
- examples are sodium bicarbonate, sodium carbonate, ammonium carbonate, ammonium bicarbonate with or without organic or inorganic acid (eg acetic acid, citric acid, oxalic acid, tartaric acid or keto-acid, or hydroxy acids such as lactic acid, etc), or NaAI(SO4)2, NaH2P04 or NaBH4; or C6N6, BaN6, azo compounds such as azodicarbonamide etc.
- some such as of those blowing agents such as carbonates, hydrogen carbonates and some phosphate derivatives may usefully act both as blowing agent and base in certain formulations.
- Foamed structures can be produced by simple use of hydroxide bases such as sodium hydroxide, although the mechanism of foam formation is not clear.
- additive of fillers such as inorganic particles (eg fumed silica, mica) or polymer powders or fibres e.g. polyethylene powder may increase swelling response in certain systems.
- inorganic particles eg fumed silica, mica
- polymer powders or fibres e.g. polyethylene powder
- hydrophilic fibre water soluble fibre or hydrophilic surface treated fibre can help to increase swell response in certain formulations.
- examples include ground cellulosic fibres, polyvinyl alcohol fibre.
- oligomer with radiation polymerisation functionality and phosphoric acid/ester helps to increase adherability to certain substrates.
- examples are phosphoric acid diacrylate, hydroxymethylmethacrylate-phosphate and styrene phosphonic acid.
- the composition may further comprise a crosslinking agent, such as a low molecular weight multifunctional (meth) acrylate.
- a crosslinking agent such as a low molecular weight multifunctional (meth) acrylate.
- Known crosslinking agents which may be used in the present composition include methylene bis acrylamide, ethylene glycol di-(meth)acrylate, di- (meth)acrylamide, cyanomethyl(meth)acrylate or vinyloxyethyl(meth)acry!ate.
- a preferred cross linking agent is pentaerythritol triacrylate.
- the amounts of crosslinking agent may be in the range of 100 to 2000 ppm, preferably in the range of 200 to 1200 ppm.
- the type of radiation used to cure the composition may be any suitable source of radiation such as infra-red, ultra-violet or heat radiation.
- a preferred form of radiation is ultra-violet.
- composition may be prepared in a multi-step process comprising the initial production of the polymer backbone, functionalisation of the polymer backbone by the addition of unsaturated bonds along the polymer backbone, isolation of this intermediate and mixing with the monomer in which the prepolymer is to be dissolved, optionally with the addition of one or more photonitiators and/or photosensitisers.
- the preparation of the ethylenically unsaturated functionalised prepolymer may be carried out in any number of standard ways.
- the polymer backbone may be prepared by polymerisation of the monomer or monomers, preferably in an aprotic solvent, using an appropriate initiator.
- Known initiators include peroxy type initiators and azo type initiators.
- Luperox IIM75 "RTM” or tertiary- butyl perpivalate may be used with cationic monomers and Vazo 67 "RTM” may be used with anionic monomers.
- the polymer backbone is functionalised by introducing unsaturated groups into the polymer backbone. Functionalisation occurs via the substitution of a hydrogen on the polymer backbone, so an aprotic solvent is preferably used.
- Preferred solvents include ethyl acetate and butyl acetate.
- a preferred method of functionalisation is the reaction of acryloyl chloride with an amine group of the polymer backbone.
- the solvent is removed by any standard method.
- a method may include the addition of an inhibitor, the application of a vacuum to the prepolymer/solvent mixture to remove the solvent, then the addition of water.
- the organic acid may be added.
- the water may be removed resulting in a liquid prepolymer, preferably all of the water is removed resulting in a solid prepolymer.
- the water may be removed by any standard procedure, including spray drying and the use of dry nitrogen.
- the solvent removal and drying steps may be combined by spray drying the prepolymer directly from the solvent.
- the solid prepoymer is preferably ground in order to reduce the particle size and aid the prepolymer dissolution.
- the functionalised prepolymer is then dissolved in the monomer, and any photoinitiators or photosensitisers may also be added.
- a further aspect of this invention is a composition comprising:
- composition may additionally comprise:
- composition may further comprise:
- crosslinking agent a crosslinking agent.
- Other possible additives include coupling agents, air release agents, inhibitors, wetting agents, lubricants or waxes, stabilisers, antioxidants and pigments.
- compositions of desirable formulations will depend on a number of factors including the required processing speed, coating thickness, water swelling or blocking response in terms of speed and extent, the nature of the surfaces to which the coating is to be applied, and the nature of solutions in which it is required to function (ie absorb).
- the radiation polymerisable polymer and its method of preparation has been described previously.
- the other components have also been previously described.
- the composition may comprise between 10 to 100 % of the prepolymer, based on the total weight of the composition.
- the preparation of the ethylenically unsaturated functionalised prepolymer may be carried out in any number of standard ways.
- the polymer backbone may be prepared by polymerisation of the monomer or monomers, preferably in an aprotic solvent, using an appropriate initiator.
- Known initiators include peroxy type initiators and azo type initiators.
- Luperox IIM75 "RTM” or tertiary- butyl perpivalate may be used with cationic monomers and Vazo 67 "RTM” may be used with anionic monomers.
- the polymer backbone is functionalised by introducing unsaturated groups into the polymer backbone. Functionalisation occurs via the substitution of a hydrogen on the polymer backbone, so an aprotic solvent is preferably used.
- Preferred solvents include ethyl acetate and butyl acetate.
- a preferred method of functionalisation is the reaction of acryloyl chloride with an amine group of the polymer backbone.
- the solvent is removed by any standard method. Such a method may include the addition of an inhibitor, the application of a vacuum to the prepolymer/solvent mixture to remove the solvent, then the addition of water. Before, during or after the removal of the solvent, the organic acid may be added. Subsequently the water may be removed resulting in a liquid prepolymer, preferably all of the water is removed resulting in a solid prepolymer.
- the water may be removed by any standard procedure, including spray drying and the use of dry nitrogen. The solvent removal and drying steps may be combined by spray drying the prepolymer directly from the solvent.
- the solid prepoymer is preferably ground in order to reduce the particle size and aid the prepolymer dissolution.
- the functionalised prepolymer is then dissolved in water, and any photoinitiators or photosensitisers may also be added.
- the compsitions may be applied to articles which contain water sensitive material within a more durable exterior, which is prone to fracture, rupture or developing fissures through which water can be transmitted.
- the composition may be applied to a cable, the cable being surrounded by a plastic coating that may fracture allowing ingress of moisture.
- the composition may be applicable to articles that comprise one or more of the group consisting of glass, plastic, rubber and metal. Generally the composition is of particular value when the article is a sheet,a fibre or a cable.
- the composition may be used to coat fibres (eg glass fibres; yarns), wires, or rods (eg cable tension members) or tubes (eg polymeric cable jackets or buffer tubes) or other articles.
- the compositions can be coated and cured on cable components (wave guide, tension member, buffer tubes, wrappings, tapes etc.) at a range of thickness of 0.001 inch up to 0.2 inches.
- compositions can have a range of swell response time from in seconds to minutes after it comes into contact with water.
- This coating (cured composition) can swell, for example, at a range of 8 times or more over original thickness. Swell heights in excess of 60 times the original thickness are possible.
- compositions may be used as a water absorbent coating or as a gel blocking agent which will absorb water to form a gel which prevents further ingress of water.
- the product is a 30% aqueous solution of a 20,000 molecular weight copolymer, comprising about 50% N.N- dimethylacrylamide and 50% tertiary-butylaminoethyl methacrylate in the form of a citric acid salt, functionalised with an average of 5 vinyl groups per polymer chain.
- Example 3 The aqueous solution from example 1 is dried under a nitrogen blanket and then ground using a pestle and mortar. The solid is then dissolved in N,N,-dimethylacrylamide to form a 30% by weight solution, based on the weight of the total formulation. The solution is then mixed with 10% by weight of the total formulation, of DARACUR 1173 "RTM".
- Example 3 The aqueous solution from example 1 is dried under a nitrogen blanket and then ground using a pestle and mortar. The solid is then dissolved in N,N,-dimethylacrylamide to form a 30% by weight solution, based on the weight of the total formulation. The solution is then mixed with 10% by weight of the total formulation, of DARACUR 1173 "RTM".
- Example 3 Example 3
- the composition from example 2 is coated onto Melinex 542 "RTM" at a thickness of 24 microns using a K-Bar Number 3. This coated sample is then passed under a lab scale UV lamp twice, at a line speed of 10 metres per second. After this curing step, an 80 mm 2 circle is cut from the sample, and placed, coated side up, into a swelling cup of internal diameter 82 mm 2 . A 80 mm 2 circle of chemically bonded non woven polyethylene is then placed on top of the sample. A piston is inserted into the cup, which is free to move. The swelling cup assembly is then placed into a digital micrometer, such as a MT25B Micrometer with an ND221 Digital Display unit, and the readout is set to zero. 100 cm 3 of deionised water is placed into the swelling cup, and then the swell height is measured with time.
- a digital micrometer such as a MT25B Micrometer with an ND221 Digital Display unit
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2001276347A AU2001276347A1 (en) | 2000-06-07 | 2001-05-25 | Water swellable compositions |
BR0111504-9A BR0111504A (en) | 2000-06-07 | 2001-05-25 | Water swellable compositions |
US10/276,843 US6797768B2 (en) | 2000-06-07 | 2001-05-25 | Water swellable compositions |
EP01953959A EP1287049A1 (en) | 2000-06-07 | 2001-05-25 | Water swellable compositions |
JP2002501980A JP2003535932A (en) | 2000-06-07 | 2001-05-25 | Water swellable composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0013839.6 | 2000-06-07 | ||
GBGB0013839.6A GB0013839D0 (en) | 2000-06-07 | 2000-06-07 | Water swellable compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001094433A1 true WO2001094433A1 (en) | 2001-12-13 |
Family
ID=9893143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/005994 WO2001094433A1 (en) | 2000-06-07 | 2001-05-25 | Water swellable compositions |
Country Status (9)
Country | Link |
---|---|
US (1) | US6797768B2 (en) |
EP (1) | EP1287049A1 (en) |
JP (1) | JP2003535932A (en) |
CN (1) | CN1216924C (en) |
AU (1) | AU2001276347A1 (en) |
BR (1) | BR0111504A (en) |
GB (1) | GB0013839D0 (en) |
WO (1) | WO2001094433A1 (en) |
ZA (1) | ZA200209879B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7026373B2 (en) | 2002-05-06 | 2006-04-11 | Stockhausen Gmbh | Polyamphoteric superabsorbent copolymers |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0013845D0 (en) * | 2000-06-07 | 2000-07-26 | Campbell Dussek Ltd | A cable or cable component coated with a water swellable material |
CA2549549C (en) * | 2003-12-15 | 2010-05-04 | Council Of Scientific & Industrial Research | Ph sensitive polymer and process for preparation thereof |
CA2549539C (en) * | 2003-12-15 | 2013-02-12 | Council Of Scientific & Industrial Research | Taste masked pharmaceutical composition comprising ph sensitive polymer |
WO2005056619A1 (en) * | 2003-12-15 | 2005-06-23 | Council Of Scientific & Industrial Research | pH SENSITIVE POLYMER AND PROCESS FOR PREPARATION THEREOF |
US20050136114A1 (en) * | 2003-12-19 | 2005-06-23 | Council Of Scientific And Industrial Research | Taste masked pharmaceutical compositions comprising bitter drug and pH sensitive polymer |
US20060134054A1 (en) * | 2003-12-19 | 2006-06-22 | Council Of Scientific And Industrial Research | Polymer composition for pH dependent dissolution behavior and process for preparation thereof |
US7294347B2 (en) * | 2004-06-21 | 2007-11-13 | Council Of Scientific And Industrial Research | Coating compositions for bitterness inhibition |
US7378109B2 (en) * | 2004-12-23 | 2008-05-27 | Council Of Scientific And Industrial Research | Pharmaceutical composition for improving palatability of drugs and process for preparation thereof |
JP4907414B2 (en) * | 2006-09-29 | 2012-03-28 | 富士フイルム株式会社 | Inkjet recording method and inkjet recording apparatus |
EP1955858B1 (en) * | 2007-02-06 | 2014-06-18 | FUJIFILM Corporation | Ink-jet recording method and device |
WO2012003782A1 (en) | 2010-07-07 | 2012-01-12 | Jianmin Zhang | Compositions and methods of making and using the compositions for improving soil and/or plant growth and improved soil, improved plants, and/or improved seeds |
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US5985952A (en) * | 1998-03-23 | 1999-11-16 | Alvin C. Levy & Associates, Inc. | Radiation curable primary coating composition for an optical fiber |
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-
2000
- 2000-06-07 GB GBGB0013839.6A patent/GB0013839D0/en not_active Ceased
-
2001
- 2001-05-25 CN CN01810904.7A patent/CN1216924C/en not_active Expired - Fee Related
- 2001-05-25 WO PCT/EP2001/005994 patent/WO2001094433A1/en not_active Application Discontinuation
- 2001-05-25 BR BR0111504-9A patent/BR0111504A/en not_active Application Discontinuation
- 2001-05-25 EP EP01953959A patent/EP1287049A1/en not_active Withdrawn
- 2001-05-25 AU AU2001276347A patent/AU2001276347A1/en not_active Abandoned
- 2001-05-25 JP JP2002501980A patent/JP2003535932A/en active Pending
- 2001-05-25 US US10/276,843 patent/US6797768B2/en not_active Expired - Fee Related
-
2002
- 2002-12-05 ZA ZA200209879A patent/ZA200209879B/en unknown
Patent Citations (13)
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US3649337A (en) * | 1970-12-21 | 1972-03-14 | Ford Motor Co | Unsaturated polyester and epoxy-functional graded-rubber paint and process ii |
US4167464A (en) * | 1978-10-16 | 1979-09-11 | The B. F. Goodrich Company | Photopolymerized hydrophilic interpolymers of unsaturated carboxylic acid and esters |
US4396476A (en) * | 1979-02-01 | 1983-08-02 | Dentsply Research & Development Corporation | Blend of cross-linked polymer, swelling monomer and cross-linking agent and curing process |
US4343919A (en) * | 1980-03-10 | 1982-08-10 | The Dow Chemical Company | Addition polymerizable polyethylenic polymers having pendant acryloyl urethane groups |
US4396377A (en) * | 1980-04-07 | 1983-08-02 | Dentsply Research & Development Corporation | Dental appliances having interpenetrating polymer networks |
US4486489A (en) * | 1980-07-08 | 1984-12-04 | The B. F. Goodrich Company | Films of hydrophilic interpolymers of neutralized acrylic acid, hydroxyalkyl methacrylate or dialkylaminoalkyl (meth)acrylate and optionally a cross-linking agent |
WO1988000097A1 (en) * | 1986-07-02 | 1988-01-14 | Loctite Corporation | Radiation curable temporary solder mask |
US4942001A (en) * | 1988-03-02 | 1990-07-17 | Inc. DeSoto | Method of forming a three-dimensional object by stereolithography and composition therefore |
US5886101A (en) * | 1988-03-02 | 1999-03-23 | E. I. Du Pont De Nemours And Company | Solvent dispersible interpenetrating polymer networks |
US5985952A (en) * | 1998-03-23 | 1999-11-16 | Alvin C. Levy & Associates, Inc. | Radiation curable primary coating composition for an optical fiber |
US6042943A (en) * | 1998-03-23 | 2000-03-28 | Alvin C. Levy & Associates, Inc. | Optical fiber containing a radiation curable primary coating composition |
US6048587A (en) * | 1998-10-01 | 2000-04-11 | Ricon Resins, Inc. | Water-dispersible, radiation and thermally-curable polymeric compositions |
WO2000057433A1 (en) * | 1999-03-18 | 2000-09-28 | Ciba Specialty Chemicals Water Treatments Limited | Water miscible liquid polymer composition |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7026373B2 (en) | 2002-05-06 | 2006-04-11 | Stockhausen Gmbh | Polyamphoteric superabsorbent copolymers |
Also Published As
Publication number | Publication date |
---|---|
US6797768B2 (en) | 2004-09-28 |
BR0111504A (en) | 2003-06-24 |
US20030176518A1 (en) | 2003-09-18 |
CN1216924C (en) | 2005-08-31 |
CN1436202A (en) | 2003-08-13 |
JP2003535932A (en) | 2003-12-02 |
AU2001276347A1 (en) | 2001-12-17 |
GB0013839D0 (en) | 2000-07-26 |
EP1287049A1 (en) | 2003-03-05 |
ZA200209879B (en) | 2003-10-10 |
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